Resin structure and use thereof

ABSTRACT

Provided is a thermoplastic resin structure formed of a resin composition that comprises substantially (a) from 5 to 80% by volume of a polyolefin resin and (b) from 20 to 95% by volume of a polyphenylene sulfide resin, which is characterized in that, in morphology therein seen through electronicmicroscopy, the polyphenylene sulfide resin (b) forms a matrix phase (continuous phase) and the polyolefin resin (a) forms a disperse phase. The thermoplastic resin structure gives plastic containers, tubes and their Attached parts having good barrier properties, strength, durability and workability.

RELATED APPLICATION

This is a divisional application of prior application Ser. No.10/715,286, filed Nov. 17, 2003, now U.S. Pat. No. 6,900,272, which is adivisional of application Ser. No. 10/089,842, filed Apr. 4, 2002, nowU.S. Pat. No. 6,830,792, which is a §371 of PCT/JP00/06984, filed Oct.6, 2000, which claims priority of JP 11-290346, filed Oct. 12, 1999, JP11-358848, filed Dec. 17, 1999, and JP 2000-39191, filed Feb. 17, 2000.

TECHNICAL FIELD

The present invention relates to resin structures of good vapor and/orliquid transmission resistance, and their use. In particular, theinvention relates to resin moldings of specific transmission resistanceand workability, which are obtained by forming a specific morphology ofpolyolefin resin and polyphenylene sulfide resin (hereinafter referredto as PPS resin) and are favorable for vapor and/or liquid barrierarticles, to such resin structures favorable for containers and pipesfor storage and transportation of liquid chemicals such as oil andgasoline, to those favorable for wrapping and packaging materials andcontainers for foods and medicines, and to their use.

BACKGROUND ART

Polyolefin resins such as polyethylene and polypropylene are the mostpopular plastics that are widely used for daily necessaries, toys,machine parts, electric and electronic parts, and automobile parts. Therecent requirement increasing in the art is for gas-barrier(transmission-resistant) resin articles capable of preventing thecontents from leaking out and protecting them from the open air forensuring the safety and the storage stability of the contents and forprotecting the environment from pollution. However, since polyolefinresins are poorly resistant to liquid chemical and vapor transmissionthrough them, their use is often limited, and it is desired to improvethem.

For improving for the physical properties of such polyolefin resins,resin compositions and moldings consisting of polyolefin resin andpolyamide resin of good transmission resistance have heretofore beenproposed in the art. The method could improve the transmissionresistance of the resin compositions and moldings over that of moldingsof polyolefin resin alone, but is still unsatisfactory. Thereforedesired is a technique of further improving the transmission resistanceof polyolefin resin structures.

For fuel tanks and oil tanks for automobiles, converting metalliccontainers into plastic containers is now actively investigated, asplastics are lightweight and easy to mold and work, their designlatitude is broad, and they are easy to handle. The matter of importancewith such plastic containers is that they do not leak the contents andcan protect the contents from the open air for ensuring the safety andthe storage stability of the contents and for protecting the environmentfrom pollution. Polyethylene, polypropylene and other polyolefincontainers are the most popular plastic containers, but their barrierproperties against gasoline and other specific oils are unsatisfactory.Therefore, it is difficult to directly use them for fuel tanks and oiltanks for automobiles. For such use, in general, they are worked intomulti-layer structures by coating them with a barrier layer of resin ofhigh transmission resistance.

One typical example of the resin to form such a barrier layer ispolyamide resin (for example, as in JP-A 220738/1983). However, therecent tendency in the field of automobile fuel is being toward using amixture of gasoline and alcohol, gasohol, for which the plasticcontainers obtainable in the above-mentioned prior art areunsatisfactory in point of their barrier properties. Therefore desiredis a technique of further improving the barrier properties of plasticcontainers.

On the other hand, it is known that PPS resin has extremely good barrierproperties against liquid chemicals such as gasoline and automobile oil,and against water and carbon dioxide. Blow-molded containers and tubularstructures of such PPS resin (for example, as in JP-A 90216/1987,255832/1986, 32816/1991), and multi-layer structures with a barrierlayer formed of a specific PPS resin and a modified polyolefin (forexample, as in JP-A 190980/1994) have been proposed. However, since itsinterlayer adhesiveness to other resin is poor, PPS resin has someproblems in that its coextrusion and lamination with other resinmaterials such as polyethylene, polypropylene and other polyolefins isdifficult and its main component must be an expensive specific PPSresin. For these reasons, the application range of PPS resin is limited.

The present invention is to improve the transmission resistance ofpolyolefin resin, and its object is to provide resin structures ofspecifically improved liquid chemical and vapor transmission resistance,not detracting from the properties such as toughness, moldability andworkability intrinsic to polyolefin resin, especially to providepolyolefin-PPS resin structures favorable for vapor and/or liquidbarrier articles, and to provide multi-layer structures of goodtransmission resistance, moldability, workability, interlayeradhesiveness and toughness that are favorable to plastic containers andcan be stably and economically formed into good plastic containers.

DISCLOSURE OF THE INVENTION

We, the present inventors have studied to solve the problems notedabove, and, as a result, have found that, when a polyolefin resin and aPPS resin are mixed in a specific ratio optionally along with aninorganic filler in such a controlled manner that the PPS resin phase inmorphology in the resulting resin composition could form a dispersedconfiguration capable of being a continuous phase or a laminar (layered)phase in the shaped structure of the resin composition, then theabove-mentioned problems can be solved. On the basis of this finding, wehave reached the present invention.

Specifically, the invention provides the following:

(1) A thermoplastic resin structure formed of a resin composition thatcomprises substantially (a) from 5 to 80% by volume of a polyolefinresin and (b) from 20 to 95% by volume of a polyphenylene sulfide resin,which is characterized in that, in morphology therein seen throughelectronic microscopy, the polyphenylene sulfide resin (b) forms amatrix phase (continuous phase) and the polyolefin resin (a) forms adisperse phase;

(2) The thermoplastic resin structure of above (1), for which the blendratio of the polyolefin resin (a) and the polyphenylene sulfide resin(b) is such that the former accounts for from 55 to 80% by volume andthe latter for from 20 to 45% by volume;

(3) The thermoplastic resin structure of above (1), for which the blendratio of the polyolefin resin (a) and the polyphenylene sulfide resin(b) is such that the former accounts for from 60 to 75% by volume andthe latter for from 25 to 40% by volume;

(4) A thermoplastic resin structure formed of a resin composition thatcomprises (a) from 15 to 85% by volume of a polyolefin resin and (b)from 15 to 85% by volume of a polyphenylene sulfide resin, which ischaracterized in that, in morphology therein seen through electronicmicroscopy, both the phase of the polyphenylene sulfide resin (b) andthe phase of the polyolefin resin (a) are substantially continuousphases;

(5) A thermoplastic resin structure formed of a resin composition thatcomprises (a) from 55 to 95% by volume of a polyolefin resin and (b)from 5 to 45% by volume of a polyphenylene sulfide resin, which ischaracterized in that, in morphology therein seen through electronicmicroscopy, the polyolefin resin (a) forms a continuous phase and thepolyphenylene sulfide resin (b) forms a laminar disperse phase;

(6) The thermoplastic resin structure of any of (1) to (5), for whichthe polyolefin resin (a) is at least one selected from polyethylene,polypropylene, ethylene/α-olefin copolymers, [copolymers of (ethyleneand/or propylene) and (unsaturated carboxylic acid and/or unsaturatedcarboxylate)], and [copolymers of (ethylene and/or propylene) and(unsaturated carboxylic acid and/or unsaturated carboxylate) in which atleast a part of the carboxyl groups are modified into metal salts];

(7) The thermoplastic resin structure of any of (1) to (6), whichcontains (c) from 0.5 to 200 parts by weight, relative to 100 parts byweight of the total of the polyolefin resin (a) and the polyphenylenesulfide resin (b), of an inorganic filler;

(8) Containers for transportation or storage of liquid chemicals orgases, which are obtained by working the thermoplastic resin structureof any of (1) to (7);

(9) Attached parts for containers for transportation or storage ofliquid chemicals or gases, which are obtained by working thethermoplastic resin structure of any of (1) to (7);

(10) Moldings of the thermoplastic resin structure of any of (1) to (7),which are formed in at least one method of injection molding, injectioncompression molding or compression molding;

(11) A multi-layer structure with a barrier layer, in which the barrierlayer is formed of the thermoplastic resin structure of any of (1) to(7);

(12) The multi-layer structure of (11), wherein a neighboring layer isformed on one or both surfaces of the barrier layer, and the neighboringlayer is a thermoplastic resin layer differing from the thermoplasticresin structure that forms the barrier layer;

(13) The multi-layer structure of (12), wherein the thermoplastic resinto form the neighboring layer is at least one selected from polyolefinresins, thermoplastic polyester resins, polyamide resins, polycarbonateresins and ABS resins;

(14) The multi-layer structure of (12), wherein the thermoplastic resinto form the neighboring layer is at least one selected from polyolefinresins, thermoplastic polyester resins and polyamide resins;

(15) The multi-layer structure of (12), wherein the thermoplastic resinto form the neighboring layer is an ethylene homopolymer and/or anethylene/α-olefin copolymer having a melt flow rate of from 0.01 to 30g/10 min and a density of from 0.90 to 0.97 g/cm³;

(16) The multi-layer structure of (12), which has an adhesive layerformed between the barrier layer and the neighboring layer;

(17) The multi-layer structure of (16), wherein the adhesive layer isformed of a modified polyolefin having a degree of crystallinity of atmost 50% and containing from 0.01 to 10% by weight of an unsaturatedcarboxylic acid or its derivative grafted thereon;

(18) The multi-layer structure of (17), wherein the adhesive layercomprises from 60 to 99 parts by weight of a modified polyolefin havinga degree of crystallinity of at most 50% and containing from 0.01 to 10%by weight of an unsaturated carboxylic acid or its derivative graftedthereon, and from 1 to 40 parts by weight of a tackifier;

(19) The multi-layer structure of any of (11) to (18), which is formedthrough coextrusion;

(20) The multi-layer structure of any of (11) to (19), which is formedinto multi-layered tubes or multi-layered blow moldings throughcoextrusion.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a model of the morphology of a resin structure in which thecontinuous phase is formed of a PPS resin component (PPS) and thedisperse phase is formed of a polyolefin resin component (PO).

FIG. 2 shows a model of the morphology of a resin structure in which aPPS resin component and a polyolefin resin component both formsubstantially continuous phases.

FIG. 3 shows a model of the morphology of a resin structure in which thecontinuous phase is formed of a polyolefin resin component and thedisperse phase is formed of a large number of thin, two-dimensionallaminae (layers) of a PPS resin component.

FIG. 4 is an electronmicroscopic picture showing the morphology of theresin structure obtained in Example 8, in which the dark part is formedof a polyolefin resin component.

FIG. 5 is an electronmicroscopic picture showing the morphology of theresin structure obtained in Comparative Example 1, in which the darkpart is formed of a polyolefin resin component.

BEST MODES OF CARRYING OUT THE INVENTION

Embodiments of the invention are described below. “Weight” referred toherein means “mass”.

The polyolefin resin (a) for use in the invention is a thermoplasticresin prepared through polymerization or copolymerization of olefinssuch as ethylene, propylene, butene, isoprene, and pentene. Concretely,it includes homopolymers such as polyethylene, polypropylene,polystyrene, polyacrylate, polymethacrylate, poly-1-butene,poly-1-pentene, polymethylpentene; as well as ethylene/α-olefincopolymers, vinyl alcohol ester homopolymers, polymers prepared by atleast partially hydrolyzing vinyl alcohol ester homopolymers, [polymersobtained by at least partially hydrolyzing copolymers of (ethyleneand/or propylene) and vinyl alcohol ester], [copolymers of (ethyleneand/or propylene) and (unsaturated carboxylic acid and/or unsaturatedcarboxylate)], [copolymers of (ethylene and/or propylene) and(unsaturated carboxylic acid and/or unsaturated carboxylate) in which atleast a part of the carboxyl groups are modified into metal salts],block copolymers of conjugated diene and vinyl-aromatic hydrocarbon, andhydrogenated derivatives of the block copolymers.

Of those, preferred are polyethylene, polypropylene, ethylene/α-olefincopolymers, [copolymers of (ethylene and/or propylene) and (unsaturatedcarboxylic acid and/or unsaturated carboxylate)], and [copolymers of(ethylene and/or propylene) and (unsaturated carboxylic acid and/orunsaturated carboxylate) in which at least a part of the carboxyl groupsare modified into metal salts]; and more preferred are low-, middle- andhigh-density polyethylene, polypropylene, and ethylene/α-olefincopolymers.

Polypropylene for use herein is not specifically defined, and may be anyof isotactic, atactic or syndiotactic polypropylene. Apart from suchhomopolymers, also usable in the invention are block or randomcopolymers comprising at least 70% by weight of a propylene componentand containing some other olefin component.

Ethylene/α-olefin copolymers for use in the invention are copolymers ofethylene and at least one α-olefin having from 3 to 20 carbon atoms, inwhich, concretely, the α-olefin having from 3 to 20 carbon atomsincludes propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene,1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene,4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene,4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene,9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, andtheir combinations. Of those, preferred are α-olefins having from 3 to12 carbon atoms, as the mechanical strength of the copolymers comprisingany of them is high. The α-olefin content of the ethylene/α-olefincopolymer preferably falls between 1 and 30 mol %, more preferablybetween 2 to 25 mol %, even more preferably between 3 and 20 mol %.

The copolymers may be further copolymerized with at least onenon-conjugated diene such as 1,4-hexadiene, dicyclopentadiene,2,5-norbornadiene, 5-ethylidenenorbornene, 5-ethyl-2,5-norbornadiene,5-(1′-propenyl)-2-norbornene.

The unsaturated carboxylic acid in the [copolymers of (ethylene and/orpropylene) and (unsaturated carboxylic acid and/or unsaturatedcarboxylate)] is any of acrylic acid or methacrylic acid or theirmixture; and the unsaturated carboxylate therein includes, for example,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl anddecyl esters of such unsaturated carboxylic acids, and their mixtures.Especially preferred are ethylene/methacrylic acid copolymers, andethylene/methacrylic acid/acrylate copolymers.

Preferably, the melt flow rate (hereinafter referred to as MFR, underASTM D1238) of the polyolefin resin (a) for use in the invention fallsbetween 0.01 and 70 g/10 min, more preferably between 0.03 and 60 g/10min. If its MFR is lower than 0.01 g/10 min, the resin is unfavorablesince its flowability is not low; but if higher than 70 g/10 min, theresin is also unfavorable since its mechanical strength is low. Thepolyolefin resin of which the MFR falls within the preferred range mayalso be one prepared by thermally decomposing a polymerized polyolefinresin with an organic peroxide.

The method of preparing the polyolefin resin (a) for use in theinvention is not specifically defined, for which, for example,employable is any of radical polymerization, coordination polymerizationwith a Ziegler-Natta catalyst, anionic polymerization, or coordinationpolymerization with a metallocene catalyst.

Preferably, the polyolefin resin (a) for use in the invention ismodified with at least one compound selected from unsaturated carboxylicacids or their derivatives. The modified polyolefin resin is highlymiscible with other resin, and has the ability to well control theseparated morphology in the resulting resin composition, and, as aresult, the transmission resistance of the resin structure is improved.Using the modified polyolefin resin is one preferred embodiment of theinvention.

Examples of the unsaturated carboxylic acids or their derivatives thatserve as the modifying agent are acrylic acid, methacrylic acid, maleicacid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid,methylfumaric acid, mesaconic acid, citraconic acid, glutaconic acid,and metal salts of these carboxylic acids; and methyl hydrogenmaleate,methyl hydrogenitaconate, methyl acrylate, ethyl acrylate, butylacrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methylmethacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate,aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleicanhydride, itaconic anhydride, citraconic anhydride,endobicyclo-(2,2,1)-5-heptene-2,3-dicarboxylic acid,endobicyclo-(2,2,1)-5-heptene-2,3-dicarboxylic acid anhydride,maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide,glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate,glycidyl itaconate, glycidyl citraconate, and5-norbornene-2,3-dicarboxylic acid. Of those, preferred are unsaturateddicarboxylic acids and their anhydrides; and especially preferred aremaleic acid and maleic anhydride.

The method of introducing such an unsaturated carboxylic acid or itsderivative component into polyolefin resin is not specifically defined.For example, the essential ingredient, olefin compound may becopolymerized with an unsaturated carboxylic acid or its derivativecompound; or a non-modified polyolefin resin may be grafted with anunsaturated carboxylic acid or its derivative compound in the presenceof a radical initiator. In any of such methods, the acid or derivativecomponent may be introduced into polyolefin resin. The amount of theunsaturated carboxylic acid or its derivative component to be introducedinto polyolefin preferably falls between 0.001 and 40 mol %, morepreferably between 0.01 and 35 mol % of all the olefin monomers thatconstitute the modified polyolefin.

The PPS resin (b) for use in the invention is a polymer havingrepetitive units of the following structural formula (I):

From the viewpoint of its heat resistance, the polymer preferablycontains at least 70 mol %, more preferably at least 90 mol % of therepetitive units of the structure formula. The PPS resin may contain anyother repetitive units such as those mentioned below, within a rangesmaller than 30 mol % of all the repetitive units that constitute theresin.

The PPS polymer partly having the structure as above will have a loweredmelting point. Therefore, in case where the melting point of thethermoplastic resin not in the barrier layer of the multi-layerstructure of the invention Is low, the PPS resin of the type isadvantageous in point of its moldability.

The melt viscosity of the PPS resin for use in the invention is notspecifically defined, so far as the resin can be kneaded in melt. Ingeneral, it falls between 50 and 20000 poises (at 320° C. at a shearrate of 1000 sec⁻¹), more preferably between 100 and 5000 poises.

The PPS resin of the type can be prepared in any known method, forexample, according to the method for preparing polymers having arelatively small molecular weight, described in JP-B 3368/1970; or themethod for preparing polymers having a relatively large molecularweight, described in JP-B12240/1977 and JP-A 7332/1986. Needless-to-say,the PPS resin prepared in the manner as above for use in the inventionmay be processed in various methods. For example, it may be heated inair for crosslinking it and/or increasing its molecular weight; or maybe heated in an inert gas atmosphere such as nitrogen or under reducedpressure; or may be washed with any of organic solvents, hot water oraqueous acid solutions; or may be activated with any of functionalgroup-having compounds such as acid anhydrides, amines, isocyanates andfunctional group-having disulfide compounds.

One concrete method of heating the PPS resin for crosslinking it and/orincreasing its molecular weight comprises heating it in an oxidizing gasatmosphere such as air or oxygen or in a mixed gas atmosphere comprisingthe oxidizing gas and an inert gas such as nitrogen or argon, in acontainer heated at a predetermined temperature so that its meltviscosity reaches the desired level. The temperature for the heattreatment generally falls between 170 and 280° C., but preferablybetween 200 and 270° C. The time for the heat treatment generally fallsbetween 0.5 and 100 hours, but preferably between 2 and 50 hours. Bycontrolling both the two, the melt viscosity of the resin can reach thedesired level. The device for the heat treatment may be any ordinary hotair drier or may be a rotary heating device or a heating device equippedwith a stirring blade. For efficiently and more uniformly heating theresin therein, preferred is a rotary heating device or a heating deviceequipped with a stirring blade.

One concrete method of heating the PPS resin in an inert gas atmospheresuch as nitrogen or under reduced pressure comprises heating it in aninert gas atmosphere such as nitrogen or under reduced pressure, at atemperature falling between 150 and 280° C., preferably between 200 and270° C., for a period of time falling between 0.5 and 100 hours,preferably between 2 and 50 hours. The device for the heat treatment maybe any ordinary hot air drier or may be a rotary heating device or aheating device equipped with a stirring blade. For efficiently and moreuniformly heating the resin therein, preferred is a rotary heatingdevice or a heating device equipped with a stirring blade.

Preferably, the PPS resin for use in the invention is deionized. Fordeionizing it, concretely, the resin may be washed with any of aqueousacid solutions, hot water, or organic solvents. Two or more thesetreatments may be combined.

One concrete method of washing the PPS resin with an organic solvent isdescribed. The organic solvent to be used for washing the resin is notspecifically defined, and may be any and every one not having thefunction of decomposing the PPS resin. For example, it includesnitrogen-containing polar solvents such as N-methylpyrrolidone,dimethylformamide, dimethylacetamide; sulfoxide or sulfone solvents suchas dimethyl sulfoxide, dimethyl sulfone; ketone solvents such asacetone, methyl ethyl ketone, diethyl ketone, acetophenone; ethersolvents such as dimethyl ether, dipropyl ether, tetrahydrofuran;halogen-containing solvents such as chloroform, methylene chloride,trichloroethylene, dichloroethylene, dichloroethane, tetrachloroethane,chlorobenzene; alcohol or phenol solvents such as methanol, ethanol,propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol,cresol, polyethylene glycol; and aromatic hydrocarbon solvents such asbenzene, toluene, xylene. Of those organic solvents, preferred areN-methylpyrrolidone, acetone, dimethylformamide, and chloroform. One ormore such organic solvents may be used either singly or as combined. Forwashing the PPS resin with such an organic solvent, for example, theresin may be dipped in the solvent, optionally stirred or heatedtherein. The temperature at which the PPS resin is washed with such anorganic solvent is not specifically defined, generally falling betweenroom temperature and 300° C. or so. The washing efficiency is higher ata higher washing temperature, but, in general, temperatures fallingbetween room temperature and 150° C. or so are enough for good washingresults. After thus washed with such an organic solvent, the PPS resinis preferably washed a few times with water or warm water to remove theorganic solvent remaining in the resin.

One concrete method of washing the PPS resin with hot water isdescribed. For the desired chemical change in the PPS resin washed withhot water, the water to be used is preferably distilled water ordeionized water. Concretely, in general, a predetermined amount of thePPS resin is put into a predetermined amount of water, and heated undernormal pressure or in a pressure container with stirring. Regarding theratio of the PPS resin to water, it is desirable that the amount ofwater is larger than that of the resin. In general, the bath ratio is soselected that at most 200 g of the PPS resin is put in one liter ofwater.

One concrete method of processing the PPS resin with acid is described.For example, the PPS resin is dipped in acid or an aqueous solution ofacid, optionally stirred or heated. The acid to be used is notspecifically defined, so far as it does not decompose the PPS resin. Forexample, it includes aliphatic saturated monocarboxylic acids such asformic acid, acetic acid, propionic acid, butyric acid;halo-substituted, aliphatic saturated carboxylic acids such aschloroacetic acid, dichloroacetic acid; aliphatic unsaturatedmonocarboxylic acids such as acrylic acid, crotonic acid; aromaticcarboxylic acids such as benzoic acid, salicylic acid; dicarboxylicacids such as oxalic acid, malonic acid, succinic acid, phthalic acid,fumaric acid; inorganic acidic compounds such as sulfuric acid,phosphoric acid, hydrochloric acid, carbonic acid, silicic acid. Ofthose, preferred are acetic acid and hydrochloric acid. Theacid-processed PPS resin is preferably washed a few times with water orwarm water for removing the acid or salt remaining in the resin. Thewater to be used for the washing treatment is preferably distilled wateror deionized water not interfering with the desirable chemical change inthe acid-processed PPS resin.

The resin composition of the invention may additionally contain anyknown compatibilizer having the function of improving the miscibility ofthe polyolefin resin (a) and the PPS resin (b) that constitute the resincomposition. Examples of the compatibilizer are organosilane compoundssuch as alkoxysilanes having at least one function group selected froman epoxy group, an amino group, an isocyanate group, a hydroxyl group, amercapto group and an ureido group; modified polyolefins such as random,block or graft copolymers of α-olefins, e.g., ethylene or propylene,with at least one compound selected from α,β-unsaturated carboxylicacids, e.g., acrylic acid, methacrylic acid, maleic acid or crotonicacid, or their derivatives, e.g., esters, anhydrides, halides or saltswith sodium, potassium, magnesium or zinc; and epoxy group-having olefincopolymers such as those comprising, as the essential ingredients,α-olefins and glycidyl esters of α,β-unsaturated acids, as well as otherpolyfunctional epoxy compounds. Two or more of these may be combined foruse herein.

The thermoplastic resin structure of the invention is characterized byits partial or entire morphology of such that (1) a PPS resin componentforms a continuous phase (matrix phase) and a polyolefin resin componentforms a disperse phase (for example, like a sea-island configuration),or (2) a PPS resin component and a polyolefin resin component both formsubstantially continuous phases (for example, like a sea-seaconfiguration), or (3) the continuous phase is formed of a polyolefinresin component and the disperse phase is formed of a large number ofthin, two-dimensional laminae (layers) of a PPS resin component (like alaminar configuration). The shape of the structure is not specificallydefined. In different sites of the structure, the morphology (1), (2) or(3) may be present together, or may appear twice or more. The morphology(1), (2) or (3) can be seen and confirmed through scanning ortransmission electronic microscopy.

The blend ratio of the polyolefin resin (a) and the PPS resin (b) thatconstitute the thermoplastic resin structure of the invention isdescribed. In case where the PPS resin component forms a continuousphase (matrix phase) and the polyolefin resin component forms a dispersephase in the morphology of the structure (for example, like a sea-islandconfiguration as in FIG. 1), the polyolefin resin accounts for from 5 to80% by volume and the PPS resin for from 20 to 95% by volume.Preferably, the polyolefin resin accounts for from 55 to 80% by volumeand the PPS resin for from 20 to 45% by volume. In that case where theamount of the PPS resin component is small, the morphology in which thePPS resin forms a continuous phase can be formed, for example, bysuitably controlling the melt viscosity ratio of polyolefin resin/PPSresin. The moldings having the morphology have a good balance of wetcharacteristics and transmission resistance and, when they are used forthe barrier layer in multi-layer structures, they also have a goodbalance of toughness, interlayer adhesiveness, barrier properties andcost. Therefore, they are extremely favorable. More preferably, theblend ratio of the two components is such that the polyolefin resinaccounts for from 60 to 75% by volume and the PPS resin for from 25 to40% by volume. If the polyolefin resin component (a) is larger than 80%by volume, the PPS resin component could hardly form the continuousphase characteristic of the resin moldings of the invention, and theobject of the invention cannot be attained. On the other hand, if thepolyolefin resin component (a) is smaller than 5% by volume, it isunfavorable since the resin moldings could not be tough and themulti-layer structures could not have good interlayer adhesiveness.

In case where the PPS resin component and the polyolefin resin componentboth form substantially continuous phases (matrix phases) in themorphology of the resin structure (for example, like a sea-seaconfiguration as in FIG. 2), it is important that the melt viscosity andthe compatibility of the polyolefin resin and the PPS resin arecontrolled within a composition range of such that the polyolefin resinaccounts for from 15 to 85% by volume and the PPS resin for from 15 to85% by volume. For embodying the separated morphology in that manner,the blend ratio of the two components is preferably such that thepolyolefin resin accounts for from 30 to 70% by volume and the PPS resinfor from 30 to 70% by volume, more preferably such that the polyolefinresin accounts for from 35 to 65% by volume and the PPS resin for from35 to 65% by volume. If the polyolefin resin component (a) is largerthan 85% by volume, the PPS resin component could hardly form asubstantially continuous phase, and structures that attain the object ofthe invention could not be obtained.

For forming the morphology in which the polyolefin resin component formsa continuous phase (matrix phase) and the PPS resin component forms alarge number of thin, two-dimensional laminae (layers) of a dispersephase (a laminar structure as in FIG. 3), the polyolefin resin accountsfor from 55 to 95% by volume and the PPS resin for from 5 to 45% byvolume. Preferably, the polyolefin resin accounts for from 60 to 90% byvolume and the PPS resin for from 10 to 40% by volume; more preferably,the polyolefin resin accounts for from 65 to 85% by volume and the PPSresin for from 15 to 35% by volume. If the polyolefin resin component(a) is larger than 95% by volume, the laminar disperse phase of the PPSresin component could not be prolonged to have a desired length and adesired weight, and the object of the invention cannot be attained. Ifthe polyolefin resin component (a) is smaller than 55% by volume, thePPS resin component could hardly form a laminar disperse phase.

L/T (length/thickness) of the PPS resin component that forms the laminardisperse phase is preferably at least 30. More preferably, L/T is atleast 100, even more preferably at least 150. If L/T is smaller than 30,structures having the desired barrier properties could not be obtained.The uppermost limit of L/T is not specifically defined, but ispreferably at most 1×10⁶ in practical use.

The inorganic filler (c) usable in the invention is not specificallydefined, and may be any fibrous, tabular, powdery or granular filler.Concretely, for example, it includes fibrous or whisker fillers such asglass fibers, PAN or pitch-type carbon fibers, metal fibers, e.g.,stainless steel fibers, aluminium fibers or brass fibers, organicfibers, e.g., aromatic polyamide fibers, and gypsum fibers, ceramicfibers, asbestos fibers, zirconia fibers, alumina fibers, silica fibers,titanium oxide fibers, silicon carbide fibers, rock wool, potassiumtitanium whiskers, barium titanate whiskers, aluminium borate whiskers,silicon nitride whiskers; and powdery, granular or tabular fillers suchas mica, talc, kaolin, silica, calcium carbonate, glass beads, glassflakes, glass microballoons, clay, molybdenum disulfide, wollastonite,titanium oxide, zinc oxide, calcium polyphosphate, graphite. Of thosefillers, preferred are glass fibers, as well as PAN carbon fibers forelectroconductive structures. The type of the glass fibers for useherein is not specifically defined, and may be any ones generally usedfor reinforcing resin. For example, they may be in any form of longfibers or short fibers of chopped strands or milled fibers. As combined,two or more different types of fillers mentioned above may be usedherein. On its surface, the filler for use in the invention may beprocessed with a known coupling agent (e.g., silane coupling agent,titanate coupling agent), or with any other surface-treating agent.Glass fibers serving as the filler may be coated or bundled withthermoplastic resin such as ethylene/vinyl acetate copolymer or withthermosetting resin such as epoxy resin.

The filler content of the resin composition preferably falls between 0.5and 200 parts by weight, more preferably between 5 and 200 parts byweight, even more preferably between 10 and 150 parts by weight relativeto 100 parts by weight of the total of the polyolefin resin (a) and thePPS resin (b).

The multi-layer structure of the invention is formed by laminatingdifferent types of resin layers, in which at least one layer(hereinafter referred to as a barrier layer (α)) is formed of thethermoplastic resin structure having the specific morphology as above,or a resin layer (hereinafter referred to as a neighboring layer (β))differing from the barrier layer is formed on at least one surface of alayer of the thermoplastic resin structure of the invention having adifferent composition or morphology (this is also a barrier layer) orthe barrier layer. In one preferred embodiment of the multi-layerstructure of the invention, an adhesive, co-extrudable resin layer(hereinafter referred to as an adhesive layer (γ)) is suitably formedbetween the barrier layer (α) and the neighboring layer (β) forenhancing the adhesiveness between the two layers. Concretely, forexample, the layer configuration of the multi-layer structure of thetype includes a two-resin two-layer configuration of layer (α)/layer(β); a two-rein three-layer configuration of layer (β)/layer (α)/layer(β); a three-resin three-layer configuration of layer (β)/layer(γ)/layer (α); a three-resin four-layer configuration of layer (β)/layer(γ)/layer (α) layer (β); and a three-resin five-layer configuration oflayer (β)/layer (γ)/layer (α)/layer (γ)/layer (β), to which, however,the invention is not limited.

The resin to form the neighboring layer (β) in the multi-layer structureof the invention is a thermoplastic resin of which the morphology andthe composition differ from the requirements in the invention. The typeof the thermoplastic resin is not specifically defined, and may be anyone selected in accordance with the use and the object of themulti-layer structure. Its examples are saturated polyester resins,polysulfone resins, polyethylene tetrafluoride resins, polyetherimideresins, polyamidimide resins, polyamide resins, polyimide resins,polycarbonate resins, polyether sulfone resins, polyether ketone resins,polythioether ketone resins, polyether-ether ketone resins,thermoplastic polyurethane resins, polyolefin resins, ABS resins,polyamide elastomers, and polyester elastomers. Two or more of these maybe combined for use herein. Of those, especially preferred arepolyolefin resins, thermoplastic polyester resins, polyamide resins,polycarbonate resins and ABS resins.

Preferred examples of the polyolefin resins may be the same as those ofthe component (a) mentioned hereinabove. Above all, especially preferredare low-, middle- and high-density polyethylene, polypropylene,ethylene/α-olefin copolymer, poly-4-methylpentene-1, chloropolyethylene,and chloropolypropylene; and more preferred are ethylene homopolymerand/or ethylene/α-olefin copolymer having a melt flow rate of from 0.01to 30 g/10 min and a density of from 0.90 to 0.97 g/cm³.

Preferred examples of the thermoplastic polyesters are those obtainedfrom dicarboxylic acids such as terephthalic acid and aliphatic diols.The dicarboxylic acids except terephthalic acid for the polyesters are,for example, aliphatic dicarboxylic acids having from 2 to 20 carbonatoms, such as azelaic acid, sebacic acid, adipic acid,decanedicarboxylic acid; aromatic dicarboxylic acids such as isophthalicacid, naphthalenedicarbbxylic acid; and alicyclic dicarboxylic acidssuch as cyclohexanedicarboxylic acid. One or more of these may be usedeither singly or as combined. The aliphatic diols include, for example,ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,1,4-butanediol, trimethylene glycol, 1,4-cyclohexanedimethanol, andhexamethylene glycol. Concretely, the polyesters are polyethyleneterephthalate, polypropylene terephthalate, polybutylene terephthalate,polyhexamethylene terephthalate, polycyclohexylenedimethyleneterephthalate, and polyethylene naphthalate. Of those, especiallypreferred for use herein are polybutylene terephthalate of goodmechanical strength, and copolyesters that comprise a dicarboxylic acidcomponent containing at least 60 mol %, preferably at least 70 mol % ofterephthalic acid along with dodecanedicarboxylic acid and/orisophthalic acid, and a 1,4-butanediol component.

The degree of polymerization of these thermoplastic polyester resins isnot specifically defined. For example, polybutylene terephthalate andcopolyesters that are preferred for use in the invention are preferablysuch that the intrinsic viscosity thereof measured in a 0.5%orthochlorophenol solution at 25° C. falls between 0.5 and 2.5, morepreferably between 0.8 and 2.0. Polyethylene terephthalate for useherein is preferably such that its intrinsic viscosity measured in a0.5% orthochlorophenol solution at 25° C. falls between 0.54 and 1.5,more preferably between 0.6 and 1.2.

The polyamide resins preferred for use herein are, for example, thosecomprising, as the essential constituent components, amino acid, lactamor diamine, and dicarboxylic acid. Examples of the essential constituentcomponents are amino acids such as 6-aminocaproic acid,11-aminoundecanoic acid, 12-aminododecanoic acid,para-aminomethylbenzoic acid; lactams such as ε-caprolactam,ω-laurolactam; aliphatic, alicyclic or aromatic diamines such astetramethylenediamine, hexamethylenediamine,2-methylpentamethylenediamine, nonamethylenediamine,undecamethylenediamine, dodecamethylenediamine,2,2,4-/2,4,4-trimethylhexamethylenediamine,5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine,1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane,1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane,bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane,2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine,aminoethylpiperazine; and aliphatic, alicyclic or aromatic dicarboxylicacids such as adipic acid, suberic acid, azelaic acid, sebacic acid,dodecanedicarboxylic acid, terephthalic acid, isophthalic acid,2-chloroterephthalic acid, 2-methylterephthalic acid,5-methylisophthalic acid, 5-sodium-sulfoisophthalic acid,hexahydroterephthalic acid, hexahydroisophthalic acid. In the invention,nylon homopolymers or copolymers derived from these starting compoundsmay be used either singly or as combined.

Especially useful in the invention are heat-resistant and strongpolyamide resins having a melting point of not lower than 150° C.Concretely, they include polycapramide (nylon 6), polyundecanamide(nylon 11), polydodecanamide (nylon 12), polyhexamethylenadipamide(nylon 66), polycapramide/polyhexamethylenadipamide copolymer (nylon6/66), polytetramethylenadipamide (nylon 46),polyhexamethylenesebacamide (nylon 610), polyhexamethylenedodecamide(nylon 612), polyhexamethyleneterephthalamide/polycapramide copolymer(nylon 6T/6), polyhexamethylenadipamide/polyhexamethyleneterephthalamidecopolymer (nylon 66/6T),polyhexamethylenadipamide/polyhexamethylenisophthalamide copolymer(nylon 66/6I),polyhexamethylenadipamide/polyhexamethyleneterephthalamide/polyhexamethylenisophthalamidecopolymer (nylon 66/6T/6I),polyhexamethyleneterephthalamide/-polyhexamethylenisophthal amidecopolymer (nylon 6T/6I),polyhexamethyleneterephthalamide/polydodecanamide copolymer (nylon6T/12),polyhexamethyleneterephthalamide/poly(2-methylpentamethylene)terephthalamidecopolymer (nylon 6T/M5T), polyxylylenadipamide (nylon XD6),polynonamethyleneterephthalamide (nylon 9T), and their mixtures andcopolymers.

Especially preferred are copolymers having hexamethyleneterephthalamideunits, such as nylon 6, nylon 66, nylon 12, nylon 11, nylon 6/66copolymer, nylon 610, nylon 6T/66 copolymer, nylon 6T/6I copolymer,nylon 6T/6 copolymer. Also preferred in practical use are mixtures ofthese polyamide resins combined in accordance with the necessaryproperties such as moldability, heat resistance and barrier properties.

The degree of polymerization of the polyamide resins is not specificallydefined. For example, preferred are those having a relative viscosity offrom 2.0 to 7.0, more preferably from 2.5 to 6.0, measured in a 98%concentrated sulfuric acid solution having a sample concentration of0.01 g/ml at 25° C.

The thermoplastic resins to form the neighboring layer (β) may contain,if desired, additives such as plasticizer, antioxidant, nucleating agentand colorant suitable to the respective resins.

The multi-layer structure of the invention, which has a barrier layer(α) formed of the thermoplastic resin structure having a separatedmorphology specifically defined in the invention, and a neighboringlayer (β) formed on one or both surfaces of the barrier layer, can beproduced, for example, in a two-layer injection molding method. However,the multi-layer structure in the form of a film or sheet may be producedin a coextrusion molding method that comprises melting the layer-formingcompositions in separate extruders, feeding the melts into amultilayer-forming die and coextruding them through the die; or in alamination molding method that comprises separately forming a layer tobe the neighboring layer followed by melt-extruding a barrier layerthereon. The multi-layer structure for blow-molding containers such asbottles, barrels or tanks or for tabular articles such as pipes or tubesmay be produced in an ordinary coextrusion molding method. For example,two-layered blow moldings of the multi-layer structure, of which theinner layer is a barrier layer having a specific morphology as hereinand the outer layer is a neighboring layer, can be produced byseparately feeding a resin composition for the barrier layer and a resincomposition for the neighboring layer into the respective two extruders,then feeding the two resin melts into a die common thereto underpressure to form the respective circular flows integrated in such amanner that the flow for the barrier layer is inside and the flow forthe neighboring layer is outside, then coextruding them out of the die,and working the resulting laminate in an ordinary known tube-forming orblow-molding method to give the intended two-layered blow moldings.Three-layered blow moldings of the multi-layer structure can be producedin the same manner as above, but using three extruders to formthree-layered structures. For these, alternatively, usable are twoextruders to form two-resin three-layered blow moldings. Of thosemethods, preferred is the coextrusion molding method as it ensures goodinterlayer adhesiveness of the multi-layer structures produced therein.

Preferably, the multi-layer structure of the invention has an adhesivelayer (γ) suitably formed between the barrier layer (α) and theneighboring layer (β) for the purpose of further improving the impactresistance, the moldability and the interlayer adhesiveness thereof. Theresin to form the adhesive layer is not specifically defined in point ofits configuration, so far as it is adhesive to both the barrier layer(α) and the neighboring layer (β) and it is coextrudable with the twolayers. Concretely, examples of the resin are modified polyolefins suchas random, block or graft copolymers comprising an α-olefin, e.g.,ethylene or propylene, and at least one compound selected fromα,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid,maleic acid and crotonic acid, and their derivatives such as esters,anhydrides, halides and salts with sodium, potassium, magnesium or zinc;random, block or graft copolymers comprising an α-olefin such asethylene or propylene, and at least one compound selected from vinylacetate, vinyl alcohol and styrenes; copolyamide adhesives andcopolyester adhesives. Of those for the adhesive layer, preferred aremodified polyolefins having a degree of crystallinity, measured throughX-ray diffractiometry, of at most 50%, preferably at most 40% andcontaining from 0.01 to 10% by weight, preferably from 0.05 to 3% byweight of an unsaturated carboxylic acid or its derivative graftedthereon. The adhesive layer of the modified polyolefin that contains anunsaturated carboxylic acid or its derivative within the defined rangeand has a degree of crystallinity falling within the defined range ishighly adhesive to the barrier layer in the multi-layer structure. Thecompounds mentioned hereinabove for the modifying agent for thepolyolefin component (a) are preferred for the unsaturated carboxylicacid and its derivative for the modified polyolefins. Especiallypreferred are unsaturated dicarboxylic acids such as acrylic acid,methacrylic acid; dicarboxylic acid anhydrides such as maleic anhydride,itaconic anhydride; and glycidyl esters of unsaturated carboxylic acidssuch as glycidyl acrylate, glycidyl methacrylate.

One or more such modified polyolefins may be used for the adhesivelayer, either singly or as combined. The modified polyolefin mixturesshall have the degree of crystallinity and the degree of grafting eachfalling within the defined range. The mixtures may contain any othergraft-modified polyolefins of which the degree of crystallinity and/orthe degree of grafting overstep the range, and/or polyolefins notgrafted and modified.

Preferred examples of the polyolefins before grafted and modified andthose not grafted and modified are homopolymers of α-olefins having from2 to 20 carbon atoms, and copolymers of two or more different types ofsuch α-olefins. The α-olefins include, for example, ethylene, propylene,1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene,1-tetradecene and 1-octadecene. The polyolefins may be copolymerizedwith minor, for example, at most 10 mol % of any other monomers exceptα-olefins.

For the polyolefins, especially preferred are ethylene homopolymers andethylene-α-olefin random copolymers. Concretely, they are linearlow-density polyethylene (L-LDPE), ethylene-propylene copolymers, andethylene-butene copolymers. Of those, more preferred are the ethylenecopolymers having an MFR of from 0.1 to 50 g/10 min, preferably from 0.2to 20 g/10 min, a density of from 0.850 to 0.940 g/cm³, preferably from0.855 to 0.920 g/cm³, an ethylene content of from 30 to 95 mol %,preferably from 40 to 92 mol %, and a degree of crystallinity measuredthrough X-ray diffractiometry of at most 50%, preferably at most 40%.

The modified polyolefins for the adhesive layer may contain a tackifier.Concretely, the tackifier includes, for example, aliphatic hydrocarbonresins, alicyclic hydrocarbon resins prepared by hydrogenating aromatichydrocarbon resins, as well as α-pinene resins, terpene resins, rosin,modified rosins, and their mixtures. The tackifying resins are solidamorphous polymers heretofore used for tackifiers and adhesives in thefield of adhesive tapes, coating compositions and hot-melt adhesives. Ofthose, especially preferred for use herein are alicyclic hydrocarbonshaving a softening point (in ring and ball method) of from 105 to 150°C., preferably from 110 to 140° C., and having a degree of hydrogenationof aromatic nuclei of at least 80%, preferably at least 85%.Commercially-available tackifiers are also usable herein. For example,mentioned is Arakawa Chemical Industry's Arkon P-125.

The blend ratio of the modified polyolefin and the tackifier may be suchthat the modified polyolefin accounts for from 60 to 99% by weight,preferably from 80 to 95% by weight, and the tackifier accounts for from1 to 40 by weight, preferably from 5 to 20% by weight.

For making it electroconductive, the thermoplastic resin structure ofthe invention may contain an electroconductive filler and/or anelectroconductive polymer. The additives are not specifically defined.For example, the electroconductive filler may be any and every onegenerally used in ordinary resins for making them electroconductive. Itsexamples are metal powders, metal flakes, metal ribbons, metal fibers,metal oxides, electroconductive substance-coated inorganic fillers,carbon powder, graphite, carbon fibers, carbon flakes, and scaly carbon.

Examples of the metal for the metal powders, metal flakes and metalribbons are silver, nickel, copper, zinc, aluminium, stainless steel,iron, brass, chromium, and tin.

Examples of the metal for the metal fibers are iron, copper, stainlesssteel, aluminium, and brass.

The metal powders, metal flakes, metal ribbons and metal fibers may beprocessed on their surfaces with a surface-treating agent such astitanate-type, aluminium-type or silane-type agents.

Examples of the metal oxides are (antimony-doped) SnO₂, (antimony-doped)In₂O₃, and (aluminium-doped) ZnO. These may be processed on theirsurfaces with a surface-treating agent such as titanate, aluminium orsilane coupling agents.

Examples of the electroconductive substance for the electroconductivesubstance-coated inorganic fillers are aluminium, nickel, silver,carbon, (antimony-doped) SnO₂, and (antimony-doped) In₂O₃. Examples ofthe inorganic fillers to be coated with it are mica, glass beads, glassfibers, carbon fibers, potassium titanate whiskers, barium sulfate, zincoxide, titanium oxide, aluminium borate whiskers, zinc oxide whiskers,titanium oxide whiskers, and silicon carbide whiskers. For coating them,for example, employable are various methods of vacuum vapor deposition,sputtering, electroless plating or baking. The inorganic fillers may beprocessed on their surfaces with a surface-treating agent such astitanate, aluminium or silane coupling agents.

Grouped from its starting materials and production methods, carbonpowder includes, for example, acetylene black, gas black, oil black,naphthalene black, thermal black, furnace black, lamp black, channelblack, roll black, and disc black. The carbon powder for use in theinvention is not specifically defined in point of its starting materialsand production methods. For it, however, especially preferred areacetylene black and furnace black. Produced are various types of carbonpowder that differ in their characteristic parameters such as particlesize, surface area, DBP oil absorption and ash content. The carbonpowder for use in the invention is not specifically defined in point ofits characteristic parameters. However, for good balance of strength andelectroconductivity thereof, the carbon powder for use herein preferablyhas a mean particle size of at most 500 nm, more preferably fallingbetween 5 and 100 nm, even more preferably between 10 and 70 nm. Thespecific surface area (in BET method) of the carbon powder is preferablyat least 10 m²/g, more preferably at least 30 m²/g. The DBP oilabsorption thereof is preferably at least 50 ml/100 g, more preferablyat least 100 ml/100 g. The ash content thereof is preferably at most0.5% by weight, more preferably at most 0.3% by weight.

The carbon particles may be processed on their surfaces with asurface-treating agent such as titanate-type, aluminium-type orsilane-type agents. For better processability in melt kneading, thecarbon powder may be formed into granules.

The moldings obtained by fabricating the thermoplastic resin structureof the invention are often desired to have good surface smoothness. Fromthis viewpoint, desired for the electroconductive fillers for use in theinvention are powdery, granular, tabular or flaky matters as well asfibrous matters that have a ratio of length/diameter of at most 200 inthe resin composition, rather than fibrous fillers having a high aspectratio, like those for the inorganic filler (c) used in the invention.

Examples of the electroconductive polymer are polyaniline, polypyrrole,polyacetylene, poly(paraphenylene), polythiophene, andpolyphenylenevinylene.

Two or more different matters of the electroconductive filler and/or theelectroconductive polymer may be used herein, as combined. Of thoseelectroconductive fillers and electroconductive polymers, especiallypreferred is carbon black as it is strong and inexpensive.

The content of the electroconductive filler and/or the electroconductivepolymer that may be in the resin structure of the invention varies,depending on the type of the electroconductive filler and/or theelectroconductive polymer to be used, and therefore could not beindiscriminately defined. However, from the viewpoint of the balance ofthe electroconductivity, the flowability and the mechanical strength ofthe resin composition, it is desirable that the filler content of theresin composition falls between 1 and 250 parts by weight, morepreferably between 3 and 100 parts by weight relative to 100 parts byweight of the total of the components (a), (b) and (c). Also morepreferably, the filler content falls between 3 and 100 parts by weightrelative to 100 parts by weight of the total of the components (a) and(b) for well making the resin structure electroconductive.

Preferably, the electroconductive resin structure has a volumeresistivity of at most 10¹⁰ Ω·cm in order that it is resistant to staticelectrification. However, the electroconductive filler and theelectroconductive polymer, if any in the resin composition, will oftenworsen the flowability of the composition and the strength of the resinstructure. Therefore, so far as the intended electroconductive level isattained, the amount of the electroconductive filler and theelectroconductive polymer to be in the resin composition is as small aspossible. The intended electroconductive level varies, depending on theuse of the resin structure. In general, the volume resistivity of theresin structure shall be larger than 100 Ω·cm but not larger than 10¹⁰Ω·cm.

The resin composition of the invention may contain any other componentsnot detracting from the effect of the invention. For example, it maycontain any of antioxidants and heat-resistant stabilizers (e.g.,hindered phenols, hydroquinones, phosphites and their substitutedderivatives), weatherproofing agents (e.g., resorcinols, salicylates,benzotriazoles, benzophenones, hindered amines), mold release agents andlubricants (e.g., montanic acid and its metal salts, esters and halfesters; stearyl alcohol, stearamide, various bisamides, bisureas,polyethylenewax), pigments (e.g., cadmium sulfide, phthalocyanine,carbon black), dyes (e.g., nigrosine), nucleating agents (e.g., talc,silica, kaolin, clay), plasticizers (e.g., octyl p-hydroxybenzoate,N-butylbenzenesulfonamide), antistatic agents (e.g., alkylsulfate-typeanionic antistatic agents, quaternary ammonium-type cationic antistaticagents, nonionic antistatic agents such as polyoxyethylene sorbitanmonostearate, betaine-type ampholytic antistatic agents), flameretardants (e.g., red phosphorus, melamine cyanurate, hydroxides such asmagnesium hydroxide and aluminium hydroxide, ammonium polyphosphate,polystyrene bromide, polyphenylene ether bromide, polycarbonate bromide,epoxy bromide resin, and combinations of such a bromine-containing flameretardant and antimony trioxide), and other polymers.

The method for producing the resin structure of the invention is notspecifically defined, so far as the resin structure produced can havethe morphology that satisfies the requirement of the invention. Forrealizing the preferred morphology, for example, the polyolefin resinand the PPS resin to form the resin structure are fed into separate twoextruders through the respective main feeders and an inorganic filler isadded thereto through a side feeder disposed at the top of eachextruder; or the polyolefin resin and the PPS resin are first kneaded inmelt, and an inorganic filler is added to the mixed resin melt.

The thermoplastic resin structure and the multi-layer structure of theinvention may be shaped in any known manner, and the method of moldingthem is not specifically defined, for which, for example, employable isinjection molding, extrusion molding, blow molding or press molding.Especially preferred for molding them is at least one method selectedfrom injection molding, injection compression molding and compressionmolding for enhancing the productivity and the industrial application ofthe invention. The molding temperature may fall generally within a rangehigher than the melting point of the PPS resin by from 5 to 50° C. Ingeneral, the moldings are single-layered, but may be multi-layered in atwo-layer molding method.

The layer configuration in the multi-layer structure of the invention isnot specifically defined. All the layers of the multi-layer structuremay be formed of the thermoplastic resin structure of the invention, orany other thermoplastic resin may be used for some layers. Intwo-layered multi-layer structures, the layer of the thermoplastic resinstructure of the invention is preferably the innermost layer in orderthat it can fully exhibit its transmission-resistant effect. Themoldings obtained herein may be integrated together or with othermoldings by the use of an adhesive or through hot-sealing, and themethod of integrating them is not specifically defined, for which areemployable any known techniques.

As the thermoplastic resin structure and the multi-layer structure ofthe invention have good gas barrier properties, and are durable and easyto work, they are favorable for containers for transportation and/orstorage of liquid chemicals and gases, for the attached parts of suchcontainers, and also for multi-layered tubes or multi-layered blowmoldings to be formed through coextrusion. Regarding the liquidchemicals and the gases, the resin structure and the multi-layerstructure are highly resistant to transmission therethrough of vaporsand/or liquids and also evaporated gases, for example, Flon-11, Flon-12,Flon-21, Flon-22, Flon-113, Flon-114, Flon-115, Flon-134a, Flon-32,Flon-123, Flon-124, Flon-125, Flon-143a, Flon-141b, Flon-142b, Flon-225,Flon-C318, R-502, 1,1,1-trichloroethane, methyl chloride, methylenechloride, ethyl chloride, methylchloroform, propane, isobutane,n-butane, dimethyl ether, castor oil-based brake fluid, glycolether-based brake fluid, borate-based brake fluid, brake fluid for usein extremely cold regions, silicone oil-based brake fluid, mineraloil-based brake fluid, power steering oil, windshield wash, gasoline,methanol, ethanol, isobutanol, butanol, nitrogen, oxygen, hydrogen,carbon dioxide, methane, propane, natural gas, argon, helium, xenon andmedicines. Therefore, the resin structure and the multi-layer structurehave many applications for parts of electric and electronic appliances,medical appliances, food-related appliances, household and office-useappliances, constructions-related parts, furniture parts and others. Forexample, their applications are for films of transmission resistanceagainst vapors and/or liquids mentioned above; as well as for tanks andbottles for automobile parts, parts for medical appliances and dailycommodities, such as air bags, bottles for liquid chemicals such asshampoo, rinse, liquid soap, detergent, tanks for storage of liquidchemicals, tanks for storage of gases, coolant tanks, oil transportationtanks, disinfectant tanks, tanks for blood transfusion pumps, fueltanks, windshield wash tanks, oil reservoir tanks, canisters; Attachedparts for such tanks and bottles, such as valves, e.g., cutoff valves,joints, gauges for attendant pumps, cases and other parts, various fueltubes and connecting parts (e.g., connectors), e.g., fuel fillerunder-pipes, ORVR hoses, reserve hoses, bent hoses, oil tubes andconnecting parts, brake hoses and connecting parts, windshield washnozzles and hoses, cooler hoses and connecting parts for cooling waterand coolant, tubes and connecting parts for coolant for airconditioners, floor-warming pipes and connecting parts, fireextinguishers and fire hoses, tubes, connecting parts and valves formedical cooling devices, tubes for transportation of liquid chemicalsand gases, containers for storage of liquidchemicals, andotherapplications requiring liquid chemical and vapor transmissionresistance; and machine parts such as automobile parts, internalcombustion engine parts, and housings for electric tools.

EXAMPLES

The invention is described in detail hereinunder with reference toExamples. However, the scope of the invention is not limited to only thefollowing Examples.

(1) Alcohol Gasoline Transmission:

Using a 40 mmφ extruder with a tubular die, a sizing die to cool thetube extruded out of the extruder and to control the size of the tubeand a take-up unit disposed at its top, a tube having an outer diameterof 8 mm and an inner diameter of 6 mm was molded. The tube was cut intoa length of 20 cm. One end of the sample was sealed up, just 6 g of analcohol gasoline mixture of commercially-available regulargasoline/ethanol of 75/25 by weight was put into it, and the other endthereof was sealed up. With that, the overall weight of the sample wasmeasured. The sample was put into an explosion-proof oven at 60° C., andkept therein for 500 hours, and its weight loss was measured.

(2) Oxygen Transmission:

Measured according to JIS K7126, method A (differential pressuremethod), for which used was GTR-10 (by Yanako Bunseki Kogyo).

(3) Mechanical Strength:

Measured according to standard methods mentioned below.

-   Tensile strength: ASTM D638-   Flexural modulus: ASTM D790-   Izod impact strength: ASTM D256    (4) Analysis of Separated Morphology:

The cross section (barrier layer) of the molded tube was analyzed withelectronic microscopes (TEM, SEM).

(5) Physical Properties of Multi-layer Structure:

(A) Gasohol Barrier Properties:

The tube was cut into a length of 30 cm. One end of the sample wassealed up, an alcohol gasoline mixture of commercially-available regulargasoline/methyl alcohol of 85/15 (by weight) was put into it, and theother end thereof was sealed up. With that, the overall weight of thesample was measured. The sample was put into an explosion-proof oven at40° C. From the weight change of the sample, the alcohol gasolinetransmission through the tube was determined.

(B) Interlayer Adhesion Strength:

The tube was cut and opened into a rectangular strip having a width of10 mm, and the inner and outer layers with an adhesive layertherebetween (the adhesive layer was stuck to the neighboring layer of athermoplastic resin composition) were peeled away by pulling them in theopposite directions at 180 degrees, whereupon the adhesion strength perthe unit length of the sample was measured.

Reference Example 1 Preparation of PPS Copolymer

3.26 kg of sodium sulfide (25 mols, containing 40% crystal water), 4 gof sodium hydroxide, 1.36 kg of sodium acetate trihydrate (about 10mols), and 7.9 kg of N-methylpyrrolidone were fed into an autoclaveequipped with a stirrer, and gradually heated up to 205° C. withstirring, and about 1.5 liters of distillate containing 1.36 kg of waterwas removed. To the residual mixture, added were 3.38 kg of1,4-dichlorobenzene (23.0 mols), 0.37 kg of 1,3-dichlorobenzene (2.5mols), and 2 kg of NMP, and heated at 265° C. for 5 hours. The reactionproduct was washed three times with hot water at 70° C., then withaqueous acetic acid solution with pH=4 at 60° C., and further four timeswith hot water at 70° C., and then dried under reduced pressure at 80°C. for 24 hours to obtain about 2 kg of a PPS copolymer resin having amelting point of 255° C. and MFR of 800 g/10 min (at 315° C. under 5000g).

The polyolefin resins and PPS used in Examples and Comparative Examplesare mentioned below. Unless otherwise specifically indicated, they wereprepared through ordinary polymerization.

<Polyolefin Resins>

-   (PO-1): high-density polyethylene having MFR of 14 and density of    0.96.-   (PO-2): high-density polyethylene having MFR of 32 and density of    0.96.-   (PO-3): polypropylene having MFR of 10 and density of 0.89.-   (PO-4): high-density polyethylene having MFR of 0.3 and density of    0.95.-   (PO-5): high-density polyethylene having MFR of 6.0 and density of    0.96.-   (PO-6): low-density polyethylene having MFR of 1.0 and density of    0.92.-   (PO-7): polypropylene having MFR of 0.5 and density of 0.89.-   (PO-8): ethylene-ethyl acrylate copolymer having MFR of 1.5 and    density of 0.93.-   (PO-9): ethylene-propylene copolymer having MFR of 0.6 and density    of 0.88.    <PPS Resins>-   (PPS-1): PPS resin having melting point of 280° C., MFR of 1000 g/10    min (at 315° C. under 5000 g) and weight-average molecular weight    (Mw) of 30000.-   (PPS-2): PPS resin having melting point of 280° C., MFR of 300 g/10    min, Mw of 49000 and viscosity of 700 poises.-   (PPS-3): PPS resin having melting point of 280° C., MFR of 100 g/10    min, Mw of 70000 and viscosity of 1700 poises.-   (PPS-4): PPS resin having melting point of 280° C., MFR of 600 g/10    min, Mw of 38000 and viscosity of 450 poises.-   (PPS-5): PPS copolymer resin prepared in Reference Example 1, having    melting point of 255° C. and MFR of 800 g/10 min.    <Thermoplastic Resins Except Resin Compositions to Form Barrier    Layer (These are for Neighboring Layer)>-   (β-1): high-density polyethylene having MFR of 0.3 g/10 min and    density of 0.94.-   (β-2): polybutylene terephthalate (Toray's LUMI CON 5201×11).-   (β-3): nylon 11 (Toray's RILSAN BESN O P40TL).-   (β-4): ethylene-1-hexene copolymer having MFR of 4 g/10 min and    density of 0.92.    <Resins for Adhesive Layer>-   (γ-1): ethylene/glycidyl methacrylate (90/10 wt. %) copolymer.-   (γ-2): ethylene/methyl acrylate/glycidyl methacrylate (64/30/6 wt.    %) copolymer.-   (γ-3): maleic anhydride-modified ethylene/1-butene copolymer (having    density of 0.88, degree of crystallinity of 15%, and degree of    grafting with maleic anhydride of 0.4% by weight).-   (γ-4): maleic anhydride-modified ethylene/1-octene copolymer (having    density of 0.86, degree of crystallinity of 5% or less, and degree    of grafting with maleic anhydride of 0.8% by weight).-   (γ-5): adhesive composition prepared by mixing maleic    anhydride-modified ethylene/1-butene copolymer (having density of    0.88, degree of crystallinity of 15%, and degree of grafting with    maleic anhydride of 0.4% by weight), maleic anhydride-modified    polyethylene (having density of 0.96 and degree of grafting with    maleic anhydride of 2.0% by weight), and tackifier (Arakawa Chemical    Industry's Arkon P-125) were mixed in a ratio of 85/5/10 parts by    weight, followed by kneading the mixture in melt in a double-screw    extruder at a cylinder temperature of 200° C.

Examples 1 to 15, Comparative Examples 1 to 4

As in Tables 1 and 2, the mixture previously prepared by melting andkneading the PPS resin and a compatibilizer (ethylene/glycidylmethacrylate copolymer, 90/10% by weight), and the polyolefin resin werefed into a double-screw extruder, Nippon Seikosho's TEX 30 Model throughits main feeder. The inorganic filler, if used, was fed thereintothrough a side feeder provided at some part of the cylinder. These werekneaded in melt in the extruder at 300° C., for which the screwrevolution was 200 rpm. The resulting pellets were dried, and theninjection-molded into test pieces. The injection-molding machine usedwas Toshiba Kikai's IS100FA, and the mold temperature was 80° C. Inaddition, the pellets prepared in the same manner as above were moldedinto tubes for the test for alcohol gasoline transmission through them.The data of the transmission resistance and the mechanical strength ofthe samples are given in Tables 1 and 2. Some samples were analyzed forthe separated morphology therein. FIG. 4 is the electronmicroscopicpicture of the sample of Example 8; and FIG. 5 is theelectronmicroscopic picture of the sample of Comparative Example 2.

In the Tables, GF is glass fibers (of 3 mm chopped strands having afiber diameter of 10 μm, by Nippon Electric Glass); MF is milled fibers(having a mean fiber length of 140 μm and a mean fiber diameter of 9 μm,by Nippon Electric Glass).

TABLE 1 Item Unit Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Constituent Type ofpolyolefin resin — PO-1 PO-2 PO-1 PO-3 PO-1 Components amount vol. % 6756 78 62 67 Type of PPS resin — PPS-2 PPS-1 PPS-1 PPS-1 PPS-1 amountvol. % 30 40 20 35 30 Compatibilizer vol. % 3 4 2 3 3 SeparatedMorphology continuous PPS PPS and polyolefin PPS PPS and phasepolyolefin matrix polyolefin matrix disperse polyolefin — PPS polyolefin— phase laminar dispersion Transmission alcohol gasoline transmission g0.5 0.7 0.8 0.6 0.6 Resistance oxygen transmission note 1 40 60 80 40 50Mechanical tensile strength MPa 45 55 40 60 45 Strength flexural modulusGPa 2.2 2.5 2.0 2.6 2.0 Izod impact strength J/m 50 56 44 42 45 Item Ex.6 Ex. 7 Ex. 8 Co. Ex. 1 Co. Ex. 2 Constituent Type of polyolefin resinPO-1 PO-4 PO-4 PO-1 PO-2 Components amount 34 57 69 100 67 Type of PPSresin PPS-2 PPS-1 PPS-2 — PPS-3 amount 60 40 30 30 Compatibilizer 6 3 1— 3 Separated Morphology PPS and polyolefin polyolefin polyolefinpolyolefin polyolefin — PPS PPS — PPS laminar laminar sphericaldispersion dispersion dispersion Transmission alcohol gasolinetransmission 0.4 0.5 0.7 3.3 2.8 Resistance oxygen transmission 15 50 9010000 9000 Mechanical tensile strength 70 40 35 30 35 Strength flexuralmodulus 2.7 2.0 1.7 1.0 1.5 Izod impact strength 40 50 46 30 28 note 1)The unit of oxygen transmission is cc · 25μ/m²24 hr · atm, 25° C.(PO-1): high-density polyethylene with MFR 14 and density 0.96. (PO-2):high-density polyethylene with MFR 32 and density 0.96. (PO-3):polypropylene with MFR 10 and density 0.89. (PO-4): high-densitypolyethylene with MFR 0.3 and density 0.95. (PPS-1): PPS resin with m.p.280° C., MFR 1000 g/10 min, and Mw 30000. (PPS-2): PPS resin with m.p.280° C., MFR 300 g/10 min, and Mw 49000. (PPS-3): PPS resin with m.p.280° C., MFR 100 g/10 min, and Mw 70000.

TABLE 2 Item Unit Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Co.Ex. 3 Co. Ex. 4 Constituent Type of — PO-1 PO-2 PO-1 PO-3 PO-1 PO-1 PO-4PO-1 PO-2 Components polyolefin resin amount vol. % 67 56 78 62 67 34 58100 67 Type of — PPS-2 PPS-1 PPS-1 PPS-1 PPS-1 PPS-2 PPS-2 — PPS-3 PPSresin amount vol. % 30 40 20 35 30 60 40 30 Compatibilizer vol. % 3 4 23 3 6 2 — 3 Type of — GF GF GF GF/talc GF/MF GF GF GF GF inorganicfiller amount wt. % 40 40 40 35/5 30/10 40 40 40 40 Separated Morphologycontinuous PPS PPS and polyolefin PPS PPS and PPS and polyolefinpolyolefin polyolefin phase polyolefin polyolefin polyolefin matrixdisperse polyolefin — PPS polyolefin — — PPS — PPS phase laminar laminarspherical dispersion dispersion dispersion Transmission alcohol g 0.40.6 0.7 0.5 0.6 0.3 0.6 3.2 2.5 Resistance gasoline transmission oxygennote 1 40 60 70 40 50 10 60 10000 9000 transmission Mechanical tensileMPa 110 110 100 95 90 115 100 100 110 Strength strength flexural GPa 6.37.0 6.1 5.5 5.2 7.8 7.3 5.4 6.0 modulus Izod impact J/m 90 100 95 90 85100 100 90 80 strength note 1) The unit of oxygen transmission is cc ·25μ/m²24 hr · atm, 25° C. (PO-1): high-density polyethylene with MFR 14and density 0.96. (PO-2): high-density polyethylene with MFR 32 anddensity 0.96. (PO-3): polypropylene with MFR 10 and density 0.89.(PO-4): high-density polyethylene with MFR 0.3 and density 0.95.(PPS-1): PPS resin with m.p. 280° C., MFR 1000 g/10 min, and Mw 30000.(PPS-2): PPS resin with m.p. 280° C., MFR 300 g/10 mm, and Mw 49000.(PPS-3): PPS resin with m.p. 280° C., MFR 100 g/10 min, and Mw 70000.

As in Examples 1 to 15 and Comparative Examples 1 to 4, the resinmoldings of the invention having a specific, separated morphology asdefined herein have good transmission resistance and confirmed thepractical applicability of the resin structure of the invention. Inaddition, the test pieces formed through injection moldings also havegood transmission resistance and confirmed the practical applicabilityof the resin structure of the invention.

Examples 16 to 32, Comparative Examples 5 to 8

As in Tables 3 to 5, the PPS resin was mixed with a compatibilizer(ethylene/glycidyl methacrylate copolymer, 90/10% by weight), theresulting mixture was fed into a double-screw extruder, NipponSeikosho's TEX 30 Model through its main feeder with the polyolefinresin being thereinto through a side feeder provided at some part of thecylinder, and these were kneaded in melt at 270 to 300° C., for whichthe screw revolution was 200 rpm. The resulting pellets were dried, andthen molded into tubes.

In that manner, molded were three-resin three-layer tubes composed ofone barrier layer (α), one neighboring layer (β) of thermoplastic resin,and one adhesive layer (γ) between the barrier layer and the neighboringlayer (or two-resin two-layer tubes not having the adhesive layer). Forthese, the molding machine used has three extruders, a forming die, asizing die and a take-up unit, in which the resin melts extruded out ofthe three extruders are collected in an adapter and molded into a tubethrough the forming die, and the tube is cooled and its size iscontrolled by the sizing die.

The three-layer tubes obtained herein had an outer diameter of 8 mm andan inner diameter of 6 mm, in which the thickness of the outer layer(thermoplastic resin layer) was 0.70 mm (in the two-layer tubes,however, this was 0.80 mm), that of the adhesive layer was 0.10 mm andthat of the inner layer (barrier layer) was 0.20 mm. The multi-layertubes were tested, and the test results are given in Tables 3, 4 and 5.

TABLE 3 Item Unit Ex. 16 Ex. 17 Ex. 18 Co. Ex. 5 Co. Ex. 6 Co. Ex. 7 Co.Ex. 8 Constituent Type of polyolefin resin — PO-4 PO-5 PO-5 — PO-5 PO-5PO-4 Components (a) of Barrier Amount of polyolefin Layer (α) resin vol.% 65 50 77 70 70 100 Type of PPS resin (b) — PPS-4 PPS-4 PPS-3 PPS-3PPS-3 PPS-3 — Amount of PPS resin vol. % 30 45 20 100 25 25Compatibilizer vol. % 5 5 3 — 5 5 — Layer (β) Thermoplastic resin layerβ-1 β-1 β-1 β-1 β-1 β-1 β-1 (neighboring layer) Layer (γ) Adhesive layerγ-1 γ-1 γ-1 γ-1 γ-1 — γ-1 Separated Morphology of Barrier Layercontinuous PPS PPS and PPS laminar PPS polyolefin polyolefin polyolefinphase polyolefin dispersion disperse polyolefin — PPS laminar — PPSspherical PPS spherical — phase dispersion dispersion dispersion Gasoholgasohol transmission 0.67 0.75 0.89 0.24 10 or more 10 or more 10 ormore Barrier (g · mm/m² · 24 h · atm) Properties Interlayer AdhesionStrength of Moldings 3.1 3.5 4.2 0.5 or less not peeled 2.2 not peeled(kg/10 mm) <Polyolefin resin> (PO-4): high-density polyethylene with MFR0.3 and density 0.95. (PO-5): high-density polyethylene with MFR 6.0 anddensity 0.96. <PPS resin> (PPS-3): PPS resin with m.p. 280° C., MFR 100g/10 min, and Mw 70000. (PPS-4): PPS resin with m.p. 280° C., MFR 600g/10 min, and Mw 38000. <Thermoplastic resin except the barrierlayer-forming resin composition> (β-1): high-density polyethylene withMFR 0.3 and density 0.94. <Adhesive layer> (γ-1): ethylene/glycidylmethacrylate copolymer.

TABLE 4 Item Unit Ex. 19 Ex. 20 Ex. 21 Ex. 22 Ex. 23 Ex. 24 ConstituentType of polyolefin resin (a) — PO-6 PO-7 PO-8 PO-9 PO-4 PO-4 ComponentsAmount of polyolefin resin vol. % 40 80 55 77 65 65 of Barrier Type ofPPS resin (b) — PPS-4 PPS-5 PPS-5 PPS-5 PPS-5 PPS-4 Layer (α) Amount ofPPS resin vol. % 60 15 40 20 30 30 Compatibilizer vol. % 5 5 5 3 5 5Layer (β) Thermoplastic resin layer β-1 β-1 β-2 β-3 β-2 β-3 (neighboringlayer) Layer (γ) Adhesive layer γ-1 γ-1 γ-1 γ-2 γ-1 γ-2 SeparatedMorphology of Barrier Layer continuous PPS polyolefin PPS and PPS andPPS PPS phase polyolefin polyolefin disperse polyolefin PPS laminar — —polyolefin polyolefin phase dispersion Gasohol gasohol transmission 0.540.82 0.63 0.75 0.70 0.56 Barrier (g · mm/m² · 24 h · atm) PropertiesInterlayer Adhesion Strength of Moldings 2.6 4.7 4.5 4.4 3.9 3.8 (kg/10mm) <Polyolefin resin> (PO-4): high-density polyethylene with MFR 0.3and density 0.95. (PO-6): low-density polyethylene with MFR 1.0 anddensity 0.92. (PO-7): polypropylene with MFR 0.5 and density 0.89.(PO-8): ethylene/ethyl acrylate copolymer with MFR 1.5 and density 0.93.(PO-9): ethylene/propylene copolymer with MFR 0.6 and density 0.88. <PPSresin> (PPS-4): PPS resin with m.p. 280° C., MFR 600 g/10 min, and Mw38000. (PPS-5): PPS copolymer resin with m.p. 255° C. and MFR 800 g/10min. <Thermoplastic resin except the barrier layer-forming resincomposition> (β-1): high-density polyethylene with MFR 0.3 and density0.94. (β-2): polybutylene terephthalate (β-3): nylon 11. <Adhesivelayer> (γ-1): ethylene/glycidyl methacrylate copolymer. (γ-2):ethylene/methyl acrylate/glycidyl methacrylate copolymer.

TABLE 5 Item Unit Ex. 25 Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex. 30 Ex. 31 Ex.32 Constituent Type of polyolefin resin (a) — PO-5 PO-4 PO-4 PO-4 PO-5PO-5 PO-4 PO-4 Components Amount of polyolefin resin vol. % 62 65 65 6550 77 65 65 of Barrier Type of PPS resin (b) — PPS-4 PPS-4 PPS-4 PPS-4PPS-4 PPS-3 PPS-5 PPS-4 Layer (α) Amount of PPS resin vol. % 35 30 30 3045 20 30 30 Compatibilizer vol. % 3 5 5 5 5 3 5 5 Layer (β)Thermoplastic resin layer β-1 β-1 β-1 β-1 β-4 β-4 β-2 β-3 (neighboringlayer) Layer (γ) Adhesive layer — γ-3 γ-4 γ-5 γ-3 γ-5 γ-5 γ-5 SeparatedMorphology of Barrier Layer continuous polyolefin PPS PPS PPS PPS andpolyolefin PPS PPS phase polyolefin disperse PPS polyolefin polyolefinpolyolefin — PPS polyolefin polyolefin phase laminar laminar dispersiondispersion Gasohol gasohol transmission 0.75 0.69 0.70 0.68 0.76 0.890.71 0.57 Barrier (g · mm/m² · 24 h · atm) Properties InterlayerAdhesion Strength of Moldings 2.0 5.2 5.0 not peeled not peeled notpeeled not peeled not peeled (kg/10 mm) <Polyolefin resin> (PO-4):high-density polyethylene with MFR 0.3 and density 0.95. (PO-5):high-density polyethylene with MFR 6.0 and density.0.96. <PPS resin>(PPS-3): PPS resin with m.p. 280° C., MFR 100 g/10 min, and Mw 70000.(PPS-4): PPS resin with m.p. 280° C., MFR 600 g/10 min, and Mw 38000.(PPS-5): PPS copolymer resin with m.p. 255° C. and MFR 800 g/10 min.<Thermoplastic resin except the barrier layer-forming resin compositon>(β-1): high-density polyethylene with MFR 0.3 and density 0.94. (β-2):polybutylene terephthalate (β-3): nylon 11. (β-4): ethylene/butenecopolymer. <Adhesive layer> (γ-3): maleic anhydride-modifiedethylene/butene copolymer. (γ-4): maleic anhydride-modifiedethylene/octene copolymer. (γ-5): maleic anhydride-modified polyolefinwith tackifier.

The multi-layer structures obtained in Examples 16 to 32, which have aseparated morphology defined in the invention, have good gasohol barrierproperties and good interlayer adhesiveness, and their practicalapplicability is good. In addition, the structures obtained in theseExamples were fabricated into multi-layer blow moldings, and they hadgood properties.

INDUSTRIAL APPLICABILITY

The thermoplastic resin structure of the invention has good vapor and/orliquid barrier properties, and has many applications in various fields.For example, it is favorable for electric and electronicappliances-related devices, precision machines-related devices,office-use appliances, automobiles and trains-related parts, buildingmaterials, wrapping and packaging materials, furniture, and dailynecessaries. In addition, the multi-layer structure of the invention hasgood barrier properties against gasohol, and gives plastic containersand tubes having the advantages of strength, durability and workability.It is favorable for gasoline tanks for automobiles, containers and pipesfor transportation and storage of liquid chemicals, and wrapping andpackaging materials and containers for foods and medicines.

1. A thermoplastic resin composition comprising (a) 55 to 95% by volumeof a polyolefin resin and (b) 5 to 45% by volume of a polyphenylenesulfide resin, based on the sum of components (a) and (b), havingmorphology as seen through electronicmicroscopy such that the polyolefinresin (a) forms a continuous phase and the polyphenylene sulfide resin(b) forms a disperse phase formed of a multiplicity of thin,two-dimensional laminae.
 2. The thermoplastic resin composition claimedin claim 1, for which the polyolefin resin (a) is at least one selectedfrom the group consisting of polyethylene, polypropylene,ethylene/α-olefin copolymers, copolymers of (ethylene and/or propylene)and (unsaturated carboxylic acid and/or unsaturated carboxylate), andcopolymers of (ethylene and/or propylene) and (unsaturated carboxylicacid and/or unsaturated carboxylate) in which at least a part of thecarboxyl groups are modified into metal salts.
 3. The thermoplasticresin composition claimed in claim 1, further comprising (c) 0.5 to 200parts by weight, relative to 100 parts by weight of the total of thepolyolefin resin (a) and the polyphenylene sulfide resin (b), of aninorganic filler.
 4. Containers for transportation or storage of liquidchemicals or gases, obtained by working the thermoplastic resincomposition of claim
 1. 5. Attached parts for containers fortransportation or storage of liquid chemicals or gases, obtained byworking the thermoplastic resin composition of claim
 1. 6. Moldings ofthe thermoplastic resin composition of claim 1, formed in at least onemethod of injection molding, injection compression molding orcompression molding.
 7. A multi-layer structure with a barrier layer, inwhich the barrier layer is formed of the thermoplastic resin compositionof claim
 1. 8. The multi-layer structure as claimed in claim 7, furthercomprising a neighboring layer formed on one or both surfaces of thebarrier layer, and the neighboring layer is a thermoplastic resin layerdiffering from the thermoplastic resin composition that forms thebarrier layer.
 9. The multi-layer structure as claimed in claim 8,wherein the thermoplastic resin to form the neighboring layer is atleast one selected from the group consisting of polyolefin resins,thermoplastic polyester resins, polyamide resins, polycarbonate resinsand ABS resins.
 10. The multi-layer structure as claimed in claim 8,wherein the thermoplastic resin forming the neighboring layer is atleast one selected from the group consisting of polyolefin resins,thermoplastic polyester resins and polyamide resins.
 11. The multi-layerstructure as claimed in claim 8, wherein the thermoplastic resin formingthe neighboring layer is an ethylenehomopolymer and/or anethylene/α-olefin copolymer having a melt flow rate of 0.01 to 30 g/10min and a density of 0.90 to 0.97 g/cm³.
 12. The multi-layer structureas claimed in claim 8, further comprising an adhesive layer formedbetween the barrier layer and the neighboring layer.
 13. The multi-layerstructure as claimed in claim 12, wherein the adhesive layer is formedof a modified polyolefin having a degree of crystallinity of at most 50%and containing 0.01 to 10% by weight of an unsaturated carboxylic acidor its derivative grafted thereon.
 14. The multi-layer structure asclaimed in claim 13, wherein the adhesive layer comprises 60 to 99 partsby weight of a modified polyolefin having a degree of crystallinity ofat most 50% and containing 0.01 to 10% by weight of an unsaturatedcarboxylic acid or its derivative graft thereon, and 1 to 40 parts byweight of a tackifier.
 15. The multi-layer structure of claim 7, whichis formed by coextrusion.
 16. The multi-layer structure of claim 7,which is formed into multi-layered tubes or multi-layered blow moldingsby coextrusion.